WO1999001489A1 - Matiere moulable thermoplastique ayant une faible couleur propre - Google Patents

Matiere moulable thermoplastique ayant une faible couleur propre Download PDF

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Publication number
WO1999001489A1
WO1999001489A1 PCT/EP1998/003836 EP9803836W WO9901489A1 WO 1999001489 A1 WO1999001489 A1 WO 1999001489A1 EP 9803836 W EP9803836 W EP 9803836W WO 9901489 A1 WO9901489 A1 WO 9901489A1
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WIPO (PCT)
Prior art keywords
weight
polymer
graft
molding compositions
thermoplastic molding
Prior art date
Application number
PCT/EP1998/003836
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German (de)
English (en)
Inventor
Norbert Güntherberg
Jürgen Koch
Peter Ittemann
Joachim Seibring
Sven Grabowski
Graham Edmund Mc Kee
Norbert Mosbach
Bernhard Czauderna
Norbert Niessner
Hartmut Heinen
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP98938632A priority Critical patent/EP0993476B1/fr
Priority to DE59803025T priority patent/DE59803025D1/de
Priority to AU87285/98A priority patent/AU8728598A/en
Priority to US09/446,982 priority patent/US6323279B1/en
Priority to BR9810666-0A priority patent/BR9810666A/pt
Priority to CA002294918A priority patent/CA2294918A1/fr
Priority to KR1020007000027A priority patent/KR100361001B1/ko
Priority to JP50626499A priority patent/JP2002510349A/ja
Publication of WO1999001489A1 publication Critical patent/WO1999001489A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters

Definitions

  • the present invention relates to thermoplastic molding compositions containing as components A) to F), based on the total weight of the molding composition,
  • a24 0 to 10, preferably 0.01 to 5 and particularly preferably 0.02 to 2% by weight of at least one polyfunctional, crosslinking monomer,
  • thermoplastic polymer C) 0 to 50% by weight of a thermoplastic polymer C) with a viscosity number VZ of 50 to 120 ml / g, based on C),
  • components B) and C) differ in their viscosity numbers VZ by at least 5 units [ml / g], or in their acrylonitrile content by at least 5 units [wt. -%] differ, or differ in both characteristics viscosity number VZ and acrylonitrile content by at least 5 units.
  • thermoplastic polymer D 0 to 95% by weight of a thermoplastic polymer D), based on D),
  • thermoplastic polymer E 0 to 50% by weight of a thermoplastic polymer E), based on E),
  • el 4 to 96% by weight of at least one vinylaromatic monomer
  • e2 4 to 96% by weight of at least one monomer selected from methyl methacrylate, maleic anhydride and maleimides
  • the invention relates to processes for the production of the thermoplastic molding compositions, the use of the thermoplastic molding compositions for the production of moldings, and finally the molding produced from the thermoplastic molding compositions.
  • Molded parts made of ABS are characterized by good mechanical properties, for example high strength and toughness, in particular - due to the low glass transition temperature Tg of polybutadiene - by good impact strength even at low temperatures.
  • ABS polymers especially those which are produced by emulsion polymerization, often have their own color, for example yellowish to brownish.
  • This intrinsic color can be expressed, for example, by the yellowness index YI, which for such ABS polymers with a distinct intrinsic color is greater than 30 to well over 50.
  • the yellow index YI depends on several factors, including the rubber content of the ABS.
  • yellowish-brown discolouration can often occur during the production of the molding compositions, their further processing into molded parts and when using the molded parts.
  • the yellowing or brown coloring is favored by high temperatures, such as those that occur during injection molding processing or mixing with additives on an extruder, and the clearer the stronger the intrinsic color of the unprocessed ABS granulate before injection molding or before extrusion.
  • the coloring of the yellowing-prone polymers is problematic because the yellow tint falsifies the desired color (lack of color fidelity) or requires the use of large amounts of expensive colorants (higher coloring costs).
  • a small depth of color is often observed with colored ABS molding compounds, caused by a high light scattering of the molding compounds. Since the initial level of the inherent color and the depth of color of the colored molded part are responsible for the color impression of the molded part, the useful value of the molding compositions is reduced in many cases by the inherent color and the yellowing.
  • EP-A 6341 teaches the processing of an acrylonitrile rubber in an extruder flushed with inert gases such as N 2 or CO 2 , which reduces the yellow tinge of the polymer. Operating an extruder under inert conditions is disadvantageous because it makes the process complex and inexpensive.
  • DE-AS 2503966 teaches ABS molding compositions whose color stability is improved by the use of a Ci-Cs alcohol during the emulsion polymerization of butadiene. The extent of
  • DE-AS 2427960 discloses ABS molding compositions whose rubber particles have been agglomerated by adding an agglomerating dispersion to the small-sized polybutadiene latex and thereby have a broad or bimodal particle size distribution.
  • DE-OS 3505749 teaches the precipitation of styrene and acrylonitrile-grafted polybutadiene rubber from its latex by adding a sulfur-containing graft product based on polybutadiene, thereby improving the thermostability of the precipitated polybutadiene rubber which has been prepared into molding compounds.
  • the high levels of sulfur compounds often lead to an unpleasant smell of the molding compounds.
  • EP-A 678531 describes ABS molding compositions with a polybutadiene graft rubber with a bimodal particle size distribution, the styrene and acrylonitrile monomers grafted onto the polybutadiene particles predominantly during the first half be metered into the monomer feed time.
  • Such ABS materials have a high toughness and good processability, but show a clear yellow tinge.
  • WO 95/22570 discloses a process for producing an ABS polymer, in which a small-sized rubber latex is produced in emulsion, partially agglomerated, and the now bimodal latex is grafted in emulsion with SAN.
  • the graft polymer is then separated from the aqueous phase and melt-mixed with a SAN matrix polymer, the AN graft shell and SAN matrix differing in their AN content by no more than 6% by weight.
  • a further partial agglomeration of the graft articles takes place.
  • Such molding compositions also have a disadvantageous yellowish inherent color.
  • molding compositions should be provided which have a low intrinsic color, that is to say a low starting level of the yellow tinge, and also have a low tendency to yellowing.
  • the molding compounds should hardly yellow even after prolonged heat storage or through processing in the heat (e.g. during injection molding or when blending on an extruder).
  • the colored molding compounds should have a high color depth, which is why the non-colored molding compound should have as little light scatter as possible.
  • the low intrinsic color desired according to the task can be characterized by a yellowness index (YI) of ⁇ 25 or an absorption of ⁇ 0.1%.
  • the desired high color depth, i.e. low light scatter, can be characterized by scatter values ⁇ 4.9.
  • Another object was to provide molding compositions whose low inherent color is not achieved at the expense of their other advantageous properties, for example mechanical properties such as toughness and rigidity, and their degree of surface gloss.
  • the task was to provide molding compositions whose mechanical properties such as toughness, o also cold toughness, and stiffness compared to the molding materials of the
  • thermoplastic molding compositions defined at the outset were found. Processes for the preparation of thermoplastic molding compositions, the use of 'the thermoplastic Forramassen for the production of moldings were and finally, the moldings produced from the thermoplastic molding compositions.
  • Component A) is a graft copolymer with a bimodal particle size distribution and is present in the molding compositions according to the invention in a proportion of 5 to 80, preferably 10 to 70 and particularly preferably 15 to 60% by weight, based on the sum of components A) and B), and - if included - C), D), E) and F).
  • the graft polymer A) is composed of a "soft" rubber-elastic, particulate graft base a1) and a "hard” graft layer a2).
  • the graft base a1) is present in a proportion of 40 to 90, preferably 45 to 85 and particularly preferably 50 to 80% by weight, based on component A).
  • the graft base a1) is obtained by polymerizing, based on a1),
  • Butadiene, isoprene, chloroprene or mixtures thereof are suitable as conjugated dienes all).
  • Butadiene or isoprene or a mixture thereof, particularly butadiene, is preferably used.
  • the constituent al) of the molding compositions may also contain further monomers al2) at the expense of the monomers all), which vary the mechanical and thermal properties of the core within a certain range.
  • monoethylenically unsaturated comonomers are:
  • vinyl aromatic monomers such as styrene, styrene derivatives of the general formula I
  • R 1 and R 2 are hydrogen or Ci-Cs-alkyl and n is 0, 1, 2 or 3;
  • Nitrogen-functional monomers such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole, vinylpyrrolidone, vinylcaprolactam, vinylcarbazole, vinylaniline, acrylamide;
  • alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, ethyl hexyl acrylate, and the corresponding Ci-Cio -Alkyl esters of methacrylic acid, and also hydroxyethyl acrylate;
  • aromatic and araliphatic esters of acrylic acid and methacrylic acid such as phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate;
  • N-substituted maleimides such as N-methyl, N-phenyl and N-cyclohexyl maleimide
  • unsaturated ethers such as vinyl methyl ether as well as mixtures of these monomers.
  • Styrene, ⁇ -methylstyrene, n-butyl acrylate or their mixtures are preferably used as monomers al2), particularly preferably styrene and n-butyl acrylate or their mixtures and very particularly preferably styrene.
  • Styrene or n-butyl acrylate or mixtures thereof are used in particular in amounts of up to 20% by weight, based on al).
  • the graft base a1) can contain crosslinking monomers a1).
  • Suitable polyfunctional, crosslinking monomers al3) are monomers with at least two ethylenically unsaturated double bonds which are not conjugated in the 1,3 position. Examples include triallyl cyanurate, divinylbenzene, divinyl esters of dicarboxylic acids such as diallyl maleate, diallyl fumarate, diallyl phthalate, allyl well - acrylate and methacrylate, dihydrodicyclopentadiene, diallyl and divinyl ethers of bifunctional alcohols such as of ethylene glycol and 1, 4 -Butandiols, diesters of polyhydric alcohols with acrylic and methacrylic such as butanediol diacrylate, ethylene glycol diacrylate, hexanediol dimethacrylate.
  • a graft base is used, based on al),
  • the graft a2) is present in a proportion of 10 to 60, preferably 15 to 55 and particularly preferably 20 to 50% by weight, based on component A).
  • the graft layers a2) are obtained by polymerizing, based on a2),
  • the vinylaromatic monomers a21) are styrene and styrene derivatives of the general formula (I)
  • R 1 and R 2 are hydrogen or -CC 8 alkyl and n is 0, 1, 2 or 3, into consideration. 15 styrene is preferably used.
  • monomers a23 which can be considered are the monomers mentioned above for component al2).
  • Methyl methacrylate and acrylates such as n-butyl acrylate are particularly suitable.
  • Methyl methacrylate MMA is very particularly suitable as monomer a23), an amount of up to 20% by weight MMA, based on a2), being preferred.
  • the graft a2) can contain crosslinking monomers a24).
  • 25 Possible polyfunctional, crosslinking monomers a24) are the monomers mentioned above for al3).
  • the graft polymers are prepared by the emulsion polymerization process. Usually one polymerizes with
  • customary emulsifiers are used, for example alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms, sulfosuccinates, ether sulfonates or resin soaps.
  • alkali metal salts of alkyl or alkylarylsulfonic acids for example alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms, sulfosuccinates, ether sulfonates or resin soaps.
  • alkali metal salts of alkyl or alkylarylsulfonic acids for example alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol s
  • alkali metal salts especially the Na and K salts, of alkyl sulfonates or fatty acids with 10 to 18 carbon atoms.
  • the emulsifiers are used in amounts of from 0.5 to 40% by weight, in particular from 0.5 to 3% by weight, based on the monomers used in the preparation of the graft base a1).
  • Sufficient water is preferably used to prepare the dispersion so that the finished dispersion has a solids content of 20 to 50% by weight. Usually a water / monomer ratio of 2: 1 to 0.7: 1 is used.
  • radical formers which decompose at the selected reaction temperature are suitable for starting the polymerization reaction, that is to say both those which decompose thermally on their own and those which do so in the presence of a redox system.
  • Possible polymerization initiators are preferably radical formers, for example peroxides, such as preferably peroxosulfates (for example sodium or potassium persulfate) and azo compounds such as azodiisobutyronitrile.
  • peroxides such as preferably peroxosulfates (for example sodium or potassium persulfate)
  • azo compounds such as azodiisobutyronitrile.
  • redox systems in particular those based on hydroperoxides such as cumene hydroperoxide, can also be used.
  • the polymerization initiators are used in an amount of 0.1 to 1% by weight, based on the graft base monomers all) and al2).
  • the radical formers and also the emulsifiers and, if applicable, the molecular weight regulators are added to the reaction batch discontinuously, for example, as a total amount at the start of the reaction, or divided into several portions, batchwise at the start and at one or more later times, or continuously during added at a certain time interval.
  • the continuous addition can also take place along a gradient, e.g. can be ascending or descending, linear or exponential, or also stepwise (stair function).
  • Molecular weight regulators such as e.g. Ethyl hexyl thioglycolate, n- or t-dodecyl mercaptan or other mercaptans, terpinols and dimeric methyl styrene or other compounds suitable for regulating the molecular weight are also used.
  • the molecular weight regulators are added to the reaction batch discontinuously or continuously, as was described above for the radical formers and emulsifiers.
  • molecular weight regulators are used in the polymerization, they can be added in the manner described above in the preparation of the graft base a1) or in the production of the graft pads a2) or in the production of a1) and a2). Details are given below regarding the grafting pads.
  • buffer substances such as Na 2 HP0 / NaH 2 P0, sodium hydrogen carbonate or buffer based on citric acid / citrate can also be used. Regulators and buffer substances are used in the usual quantities, so that further details are not necessary.
  • a reducing agent is added during the grafting of the graft base a1) with the monomers a21) to a23).
  • the graft base can also be prepared by polymerizing the monomers a1) in the presence of a finely divided latex (so-called "seed latex procedure" of the polymerization).
  • This latex is introduced and can consist of monomers forming rubber-elastic polymers, or also of other monomers, as already mentioned.
  • Suitable seed latices consist, for example, of polybutadiene or polystyrene. The polystyrene seed latex is particularly preferred.
  • the graft base a1) can be produced in the so-called inflow.
  • a certain proportion of the monomers a1) is introduced and the polymerization is started, after which the remainder of the monomers (“inflow fraction”) a1) are added as an inflow during the polymerization.
  • the feed parameters (shape of the gradient, amount, duration, etc.) depend on the other polymerization conditions. The statements made regarding the addition of the radical start or emulsifier also apply here analogously.
  • the proportion of the monomers a1) is preferably 5 to 50%, more preferably 8 to 40% by weight, based on a1).
  • the feed fraction of a1) is preferably allowed to run in within 1-18 hours, in particular 2-16 hours, very particularly 4 to 12 hours.
  • Graft polymers with several "soft” and “hard” shells e.g. of the structure al) -a2) -al) -a2), or a2) -al) -a2), especially in the case of larger particles.
  • the precise polymerization conditions are preferably chosen such that the latex of the graft polymer A obtained, an average particle size, defined by the dsrj value of the particle size distribution, of 80 to 800, is preferred 80 to 600 and particularly preferably 85 to 400.
  • the reaction conditions are coordinated with one another in such a way that the polymer particles have a bimodal particle size distribution, that is to say a size distribution with two more or less pronounced maxima.
  • the first maximum is more pronounced 5 (comparatively narrow peak) than the second and is generally 25 to 200, preferably 60 to 170, particularly preferably 70 to below 150 nm.
  • the second maximum is comparatively broad and is generally 150 to 800, preferably 180 to 700, particularly preferably 200 to 600 nm.
  • the second maximum (150 to 800 nm) is larger than the first maximum (25 to 200 nm).
  • the bimodal particle size distribution is preferably achieved by a (partial) agglomeration of the polymer particles. This can
  • the procedure is as follows:
  • the monomers a1) which form the core are polymerized up to a conversion of usually at least 90, preferably greater than 95%, based on the monomers used. This turnover is usually reached after 4 to 20 hours.
  • the rubber latex obtained has
  • ds 0 an average particle size ds 0 of at most 200 nm, preferably less than 150 nm, and a narrow particle size distribution (almost monodisperse system).
  • the rubber latex is agglomerated.
  • methacrylamide, N-methylol methacrylamide or N-vinyl pyrrolidone used.
  • a copolymer of 90 to 96% by weight of ethyl acrylate and 4 to 10% by weight of methacrylamide is particularly preferred.
  • the agglomerating dispersion can optionally also contain several of the acrylic ester polymers mentioned.
  • the concentration of the acrylic ester polymers in the dispersion used for agglomeration should generally be between 3 and 40% by weight. In the agglomeration, 0.2 to 20, preferably 1 to 5 parts by weight of the agglomeration dispersion are applied
  • the agglomeration is carried out by adding the agglomerating dispersion to the rubber.
  • the rate of addition is normally not critical, generally it takes about 1 to 60 minutes at a temperature between 20 and
  • the rubber latex can also be agglomerated by other agglomerating agents such as acetic anhydride. Agglomeration by pressure or freezing (pressure or freeze agglomeration) is also possible. The methods mentioned are known to the person skilled in the art.
  • the rubber particles Under the conditions mentioned, only a part of the rubber particles is agglomerated, so that a bimodal distribution is produced. After agglomeration there are generally more than 40, preferably between 45 and 95% of the particles (number distribution) in the non-agglomerated state.
  • the partially agglomerated rubber latex obtained is relatively stable, so that it can be easily stored and transported without coagulation occurring.
  • the polymerization of the graft base a1) is usually carried out by selecting the reaction conditions in such a way that a graft base with a specific crosslinking state results.
  • essential parameters for this are the reaction temperature and duration, the ratio of monomers, regulator, radical initiator and, for example, in the feed process, the feed rate and the amount and time of addition of regulator and initiator.
  • One method of characterizing the crosslinking state of crosslinked polymer particles is to measure the swelling index QI, which is a measure of the swellability of a more or less strongly crosslinked polymer by a solvent.
  • Typical swelling agents are, for example, methyl ethyl ketone or toluene.
  • T 2 times NMR relaxation times of the mobile protons
  • a further measure for the characterization of the graft base and its crosslinking state is the gel content, i.e. the part of the product that crosslinks and is therefore not soluble in a particular solvent. It makes sense to determine the gel content in the same solvent as the swelling index.
  • Typical gel contents of the graft bases a1) according to the invention are in the range from 50 to 90%, preferably 55 to 90% and particularly preferably 60 to 85%.
  • the swelling index is determined, for example, using the following method: approx. 0.2 g of the solid of a graft base dispersion which has been formed by evaporation of the water is swollen in a sufficiently large amount (e.g. 50 g) of toluene. After e.g. The toluene is suctioned off for 24 h and the sample is weighed out. After drying the sample in vacuo, it is weighed again.
  • the swelling index is the ratio of the weight after the swelling process to the weight dry after re-drying. Accordingly, the gel fraction is calculated from the ratio of the dry weight after the swelling step to the weight before the swelling step (x 100%)
  • the T 2 time was determined by measuring the NMR relaxation of a dewatered and filmed sample of the graft base dispersion.
  • the sample is, for example, after flashing off overnight at z. 60 ° C dried in a vacuum for 3 h and then measured at 80 ° C with a suitable measuring device, eg minispec device from Brucker. Only samples that were measured using the same method can be compared, since the relaxation is clearly temperature-dependent.
  • the graft pads a2) can be produced under the same conditions as the graft base a1), the pad a2) being able to be produced in one or more process steps.
  • a two-stage grafting it is possible first to polymerize styrene or .alpha.-methylstyrene alone and then styrene and acrylonitrile in two successive steps.
  • This two-stage grafting (first styrene, then styrene / acrylonitrile) is a preferred embodiment. Further details on the preparation of the graft polymers A) are described in DE-OS 12 60 135 and DE-OS 31 49 358.
  • graft polymerization on the graft base a1) again in an aqueous emulsion. It can be carried out in the same system as the polymerization of the graft base, and further emulsifier and initiator can be added. These need not be identical to the emulsifiers or initiators used to prepare the graft base a1). For example, it may be expedient to use a persulfate as the initiator for the preparation of the graft base a1), but to use a redox initiator system to polymerize the graft a2). For the rest, the same applies to the choice of emulsifier, initiator and polymerization auxiliaries as said in the preparation of the graft base a1).
  • the monomer mixture to be grafted on can be added to the reaction mixture all at once, batchwise in several stages or, preferably, continuously during the polymerization.
  • crosslinking monomers a24 and molecular weight regulators, as have already been described, to the polymerization of the graft layers a2).
  • the amounts are 0.001 to 5, preferably 0.005 to 2 and particularly preferably 0.01 to 2% by weight, based on the monomers a21) to a24).
  • the regulators are either distributed at the beginning of the grafting reaction or at a later point in time, or in several stages in equal or different parts evenly over the feed period, or together with the graft monomers a21) to a24) over the entire feed period or during one certain period of the inflow duration added. Al) has already been said about the method of addition.
  • a regulator can be added, for example, in the first stage and a crosslinker a24) in the second stage, or vice versa. It is also possible to use both regulators and crosslinkers in both stages, the ratio of regulator / crosslinker a24) in the stages being the same or different.
  • Component B) is a thermoplastic polymer and is present in the molding compositions according to the invention in a proportion of 20 to 95, preferably 30 to 90 and particularly preferably 40 to 85% by weight, based on the sum of components A) and B), and - if included - C), D), E) and F).
  • Component B) is obtained by polymerizing, based on B),
  • Suitable vinyl aromatic monomers b1) are styrene and styrene derivatives of the general formula (I), as described for component a21). Styrene and / or ⁇ -methylstyrene are preferably used.
  • the graft a2) of the graft polymer A) consists essentially of, based on A2,
  • thermoplastic polymer B) consists essentially of, based on B), bl) 71 to 78% by weight % Styrene, and b2) 22 to 29% by weight acrylonitrile.
  • component B) consists of two polymers B ') and B ").
  • the polymer B') corresponds to the polymer B) described above, with vinyl aromatic monomers bl ') being only those of the formula (I) with R 1 and R 2 are used equal to hydrogen, i.e. non-alkylated vinyl aromatics.
  • Styrene is preferably used as monomer bl ') in B').
  • the polymer B ") corresponds to the polymer B) described above, but only those of the formula (I) with R 1 and R 2 equal to Ci-Ca-alkyl radical, ie alkylated vinyl aromatics, are used as vinyl aromatic polymers bl").
  • the preferred monomer BL ") in B") is ⁇ -methylstyrene.
  • Polymer B " is preferably an ⁇ -methyl-styrene-acrylonitrile copolymer.
  • component B if it contains two components B ') and B"'), consists of a styrene-acrylonitrile copolymer B ') and an ⁇ -methylstyrene-acrylonitrile copolymer B ").
  • B) consists of B ') and B "
  • the ratio B') / B" is between 99: 1 and 1:99, preferably 95: 5 and 5:95.
  • the monomers mentioned further above for component al2) can be used as further monomers b3).
  • methyl methacrylate and N-alkyl or N-aryl maleimides e.g. N-phenylmaleimide suitable.
  • the polymers B which are generally referred to as SAN polymers because of their main components styrene and acrylonitrile, are known and in some cases. also commercially available.
  • Component B has a viscosity number VZ (determined from
  • Component C) is also a thermoplastic polymer and is in the molding compositions according to the invention in a proportion of 0 to 50, preferably 0 to 48 and particularly preferably 0 to
  • Component C) is obtained by polymerizing, based on C), cl) 69 to 81, preferably 71 to 78 and particularly preferably 72 to 77% by weight of at least one vinylaromatic monomer,
  • Suitable vinyl aromatic monomers cl) are styrene and styrene derivatives of the general formula (I), as described for component a21). Styrene is preferably used.
  • the monomers mentioned above for component al2) can be used as further monomers c3).
  • Methyl methacrylate, maleic anhydride and N-phenyl maleimide are particularly suitable.
  • Component C) has a viscosity number VZ of 50 to 120, preferably 52 to 110 and particularly preferably 55 to 105 ml / g. They are obtained in a known manner by bulk, solution, suspension, precipitation or emulsion polymerization, bulk and solution polymerization being preferred. Details of these methods are e.g. in the plastics handbook, ed. R. Vieweg and G. Daumiller, vol. V "Polystyrol", Carl-Hanser-Verlag Kunststoff 1969, pp. 118 ff.
  • Components B) and C) are accordingly polymers of the SAN type which contain comparatively little copolymerized acrylonitrile (maximum 31% by weight). According to the invention, B) and C) differ
  • Component D) is likewise a thermoplastic polymer and is present in the molding compositions according to the invention in a proportion of 0 to 95, preferably 0 to 80 and particularly 0 to 70% by weight, based on the sum of components A) and B ) , and - if included - C), D), E) and F).
  • Component D) is obtained by polymerizing, based on D),
  • dl 63 to less than 69, preferably 64 to 68% by weight of at least one vinylaromatic monomer
  • d3) 0 to 40, preferably 0 to 30,% by weight of at least one further, monoethylenically unsaturated monomer.
  • Suitable vinyl aromatic monomers dl) are styrene and styrene derivatives of the general formula (I) as described for component a21). Styrene and / or ⁇ -methylstyrene, in particular styrene, are preferably used.
  • the monomers mentioned above for component a21) can be used as further monomers d3).
  • Methyl methacrylate, maleic anhydride, N-phenyl maleimide and other N-substituted maleimides are particularly suitable.
  • Component D is therefore a SAN polymer, but differs from B) and C) in that it contains a small amount of vinylaromatic monomers dl) and a higher amount of acrylonitrile d2) (over 31 % By weight).
  • Component D) generally has a viscosity number VZ of 55 to 110, preferably 56 to 105 and particularly preferably 58 to 103 ml / g.
  • Component D) is obtained in a known manner by bulk, solution, suspension, precipitation or emulsion polymerization. Details of these methods are e.g. described in the plastic handbook, ed. R. Vieweg and G. Daumiller, vol. V "Polystyrol", Carl-Hanser-Verlag Kunststoff 1969, pp. 118 ff.
  • Component E) is likewise a thermoplastic polymer and is present in the molding compositions according to the invention in a proportion of 0 to 50, preferably 0 to 40 and particularly preferably 0 to 30% by weight, based on the sum of components A) and B) , and - if included - C), D), E) and F).
  • Component E) is obtained by polymerizing, based on E),
  • el 4 to 96, preferably 8 to 92 and particularly preferably 10 to 90% by weight of at least one vinylaromatic monomer, e2) 4 to 96, preferably 8 to 92 and particularly preferably 10 to
  • Suitable vinyl aromatic monomers el) are styrene and styrene derivatives of the general formula (I) as described for a21)
  • Styrene and / or ⁇ -methylstyrene are preferably used.
  • methyl methacrylate MMA is preferred.
  • Component E) is particularly preferably copolymers of styrene and maleic anhydride, or of styrene and maleimides, or of styrene, maleimides and MMA, or of styrene, maleimides and acrylonitrile, or of styrene, maleimides, MMA and Acrylonitrile.
  • the monomers el) to e3) are selected so that the polymer E) is different from the polymers B) and, if also contained in the molding compositions, C) and D).
  • the polymers E) can serve to increase the heat resistance of the thermoplastic molding compositions.
  • Component E) generally has a viscosity number VZ of 50 to 120, preferably 55 to 110 ml / g.
  • Component E) is obtained in a known manner by bulk, solution, suspension, precipitation or emulsion polymerization. Details of these methods are e.g. in the plastics handbook, ed. R. Vieweg
  • Component F are additives which contain from 0 to 50, preferably 0.1 to 45 and particularly preferably 0.2 to 35, 30% by weight, based on the sum of components A) and B), and if contained - C), D), E) and F), are contained in the thermoplastic molding compositions according to the invention.
  • Component F comprises lubricants or mold release agents, waxes, 40 pigments, dyes, flame retardants, antioxidants, stabilizers against the effects of light and heat, matting agents to achieve a matt molding surface, anti-dripping agents, fibrous and powdery fillers or reinforcing agents or antistatic agents , as well as other usual additives, such as 45 in the "Plastics Additives Handbook", Ed. Gumbleter and Müller, 4th edition, Hanser Publ., Kunststoff, 1996, or their mixtures.
  • Suitable lubricants and mold release agents are e.g. Stearic acids, stearyl alcohol, stearic acid esters or amides as well as silicone oils, montan waxes and those based on polyethylene and polypropylene.
  • Pigments are, for example, titanium dioxide, phthalocyanines, ultramarine blue, iron oxides or carbon black, as well as the entire class of organic pigments.
  • Dyes are to be understood as all dyes which can be used for the transparent, semi-transparent or non-transparent coloring of polymers, in particular those which are suitable for coloring styrene copolymers. Dyes of this type are known to the person skilled in the art.
  • flame retardants e.g. the halogen-containing or phosphorus-containing compounds known to the person skilled in the art, magnesium hydroxide and other customary compounds, or mixtures thereof, are used. Red phosphorus is also suitable.
  • Suitable antioxidants are, in particular, sterically hindered mononuclear or multinuclear phenolic antioxidants, which can be substituted in different ways and can also be bridged via substituents. In addition to monomers, this also includes oligomeric compounds, which can be made up of several phenolic base bodies. Hydroquinones and hydroquinone compounds, substituted compounds are also suitable, as are antioxidants based on tocopherols and their derivatives. Mixtures of different antioxidants can also be used. In principle, all commercially available compounds or compounds suitable for styrene copolymers can be used, such as Topanol ® or Irganox ® .
  • costabilizers can be used together with the phenolic antioxidants mentioned by way of example, in particular phosphorus- or sulfur-containing costabilizers.
  • P- or S-containing costabilizers are known to the person skilled in the art and are commercially available.
  • Suitable light stabilizers are, for example, various substituted resorcinols, salicylates, benzotriazoles, benzophenones, HALS (Hindered Amine Light Stabilizers), as they are, for example commercially available as Tinuvin ®.
  • Suitable matting agents are both inorganic substances such as talc, glass balls or metal carbonates (such as MgC0 3 , CaC0 3 ), and polymer particles - in particular spherical particles with diameters dso (weight average) over 1 ⁇ m - based on, for example, methyl methacrylate, styrene compounds, Acrylonitrile or mixtures thereof. It is also possible to use polymers which contain copolymerized acidic and / or basic monomers.
  • Suitable anti-dripping agents are, for example, polytetrafluoroethylene (Teflon®) polymers and ultra-high molecular weight polystyrene (molecular weight M w over 2,000,000).
  • fibrous or powdered fillers are carbon or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, cut glass, glass balls and wollastonite, particularly preferably glass fibers. If glass fibers are used, these can be equipped with a size and an adhesion promoter for better compatibility with the blend components. Glass fibers can be incorporated both in the form of short glass fibers and in the form of endless strands (rovings).
  • Suitable particulate fillers are carbon black, amorphous silica, magnesium carbonate (chalk), powdered quartz, mica, mica, bentonite, talc, feldspar or, in particular, calcium silicates such as wollastonite and kaolin.
  • Suitable antistatic agents are, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or alkylene amines, polyethylene glycol esters, copolymers of ethylene oxide and propylene oxide (in particular two-block or three-block copolymers of ethylene oxide and propylene oxide blocks) and glycerol mono- and distearates, and also their mixtures.
  • amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or alkylene amines
  • polyethylene glycol esters copolymers of ethylene oxide and propylene oxide (in particular two-block or three-block copolymers of ethylene oxide and propylene oxide blocks) and glycerol mono- and distearates, and also their mixtures.
  • the graft polymers with a bimodal particle size distribution are prepared by the emulsion polymerization process, as has already been described for component A).
  • the bimodal particle size distribution is adjusted by suitable measures.
  • the mentioned (partial) agglomeration of the polymer particles is achieved by adding an agglomerating dispersion of an acrylic ester polymer. merisates, preferred.
  • suitable measures known to the person skilled in the art can be taken in order to adjust the bimodal particle size distribution.
  • the resulting dispersion of the graft polymer A) can either be mixed directly with components B) to F) or it can be worked up beforehand. The latter approach is preferred.
  • the dispersion of the graft polymer A) is worked up in a manner known per se.
  • the graft polymer A) is first precipitated from the dispersion, for example by adding precipitating salt solutions (such as calcium chloride, magnesium sulfate, alum) or acids (such as acetic acid, hydrochloric acid or sulfuric acid) or by freezing (freeze coagulation).
  • precipitating salt solutions such as calcium chloride, magnesium sulfate, alum
  • acids such as acetic acid, hydrochloric acid or sulfuric acid
  • freezing freeze coagulation
  • Precipitation by high shear forces, the so-called shear precipitation is also possible, the high shear forces being generated, for example, by rotor / stator systems or by pressing the dispersion through a narrow gap.
  • the aqueous phase can be separated off in a conventional manner, for example by sieving, filtering, decanting or centrifuging.
  • This prior separation of the dispersion water gives water-moist graft polymers A) with a residual water content of up to 60% by weight, based on A), the residual water e.g. can both adhere externally to the graft polymer and can also be enclosed therein.
  • the graft polymer can then be further dried in a known manner, for example by warm air or by means of a power dryer. It is also possible to work up the dispersion by spray drying.
  • the graft polymers A) are mixed with the polymer B) and, if present, the further components C), D), E) and / or F) in a mixing device, an essentially molten polymer mixture being formed.
  • Essentially molten means that in addition to the predominant, molten (softened) fraction, the polymer mixture can also contain a certain proportion of solid constituents, for example unmelted fillers and reinforcing materials such as glass fibers, metal flakes, or unmelted pigments, dyes, etc. " Molten “means that the polymer mixture is at least viscous, ie it is at least softened to the extent that it has plastic properties. ⁇ ur
  • Mixing devices that are known to the person skilled in the art are used as mixing devices.
  • Components A) and B) and - if included - C), D), E) and F) can be mixed, for example, by extruding them together, kneading or rolling, the components A) to F) being necessary beforehand from the solution obtained in the polymerization or have been isolated from the aqueous dispersion.
  • the water or the solvent is removed from the mixing device, preferably an extruder, via a degassing unit.
  • Mixing devices for carrying out the process according to the invention are, for example, discontinuous, heated internal kneaders with or without a ram, continuously working kneaders such as continuous internal kneaders, screw kneaders with axially oscillating screws, Banbury kneaders, furthermore extruders as well as roller mills, mixing rolling mills with heated rollers and calenders.
  • An extruder is preferably used as the mixing device.
  • Single or twin-screw extruders for example, are particularly suitable for melt extrusion.
  • a twin screw extruder is preferred.
  • the mechanical energy introduced by the mixing device during mixing already causes the mixture to melt, so that the mixing device does not have to be heated. Otherwise, the mixing device is usually heated.
  • the temperature depends on the chemical and physical properties of components A) and B), and - if included - C), D), E) and F), and must be selected so that an essentially molten polymer mixture is formed. On the other hand, the temperature should not be unnecessarily high in order to avoid thermal damage to the polymer mixture.
  • the mechanical energy introduced can also be so high that the mixing device even has to be cooled.
  • the mixing device is usually operated at 150 to 300, preferably 180 to 300 ° C.
  • the graft polymer A) is mixed with the polymer B) and, if present, the further components C), D), E) and / or F) in an extruder, the dispersion of the graft polymer A ) without first separating the dispersion water directly into the extrusion which is dosed.
  • the water is usually removed along the extruder via suitable degassing devices.
  • degassing openings which are provided with retaining screws (which prevent the polymer mixture from escaping) can be used as degassing devices.
  • the graft polymer A) is mixed with the polymer B) and, if present, the further components C), D), E) and / or F), in an extruder, the graft polymer A) before, for example is separated from the dispersion water by sieving, filtering, decanting or centrifuging.
  • This prior separation of the dispersion water gives water-moist graft polymers A) with a residual water content of up to 60% by weight, based on A), the residual water e.g. can both adhere externally to the graft polymer and can also be enclosed therein.
  • the existing residual water can then, as described above, be removed as steam via degassing devices of the extruder.
  • the residual water in the extruder is not removed as steam alone, but part of the residual water is removed mechanically in the extruder and leaves the extruder in the liquid phase.
  • the polymer B) and, if present, components C), D), E) and / or F) are fed to the same extruder, so that the finished molding composition is extruded as the product of the process. This process (squeezing process) is described in more detail below:
  • the graft polymer is previously removed from the dispersion water e.g. by sieving, pressing, filtering, decanting, sedimenting, centrifuging, or by partially thermal drying.
  • the graft polymer partially dewatered in this way and containing up to 60% by weight of residual water is metered into the extruder.
  • the dosed material is conveyed by the screw against an accumulation element which acts as an obstacle and which is generally located at the end of a "squeezing section".
  • a pressure builds up in this storage zone, which presses the water out of the graft polymer (“squeezes”).
  • the pressure can be built up by arranging the screws, kneading elements or other accumulation elements differently. Basically, all commercially available device elements that serve to build up pressure are suitable. For example, as possible damming elements
  • Screw elements with a slope opposite to the conveying direction including screw elements with conveying threads with a large pitch (pitch greater than one screw diameter) opposite the conveying direction (so-called LGS elements)
  • Two or more of the baffle elements can also be combined with one another.
  • the congestion effect of the congestion zone can be adapted to the respective graft rubber by the length and the intensity of the individual congestion elements.
  • the screw elements which are located in front of the accumulation zone are generally designed as conventional screw conveyors.
  • screw conveyors are used whose incline increases in the direction of the accumulation zone, that is to say it becomes steeper. This configuration causes a comparatively slow pressure build-up - one speaks of a compression zone - which can be advantageous for the dewatering of certain rubbers.
  • the pressure build-up takes place without a previous compression zone (i.e. the auger in the squeezing section has a constant slope), i.e. immediately before or in the storage zone.
  • all the structural features and all operating parameters of the extruder are preferably matched to one another in such a way that, at the screw speed selected, the elastomeric material is conveyed and compressed, but is not or only to a minor extent plasticized or melted and not melted.
  • the squeezing section of the extruder for building up pressure preferably contains screw elements with an incline counter to the conveying direction and / or corresponding kneading blocks.
  • the water squeezed out of the graft polymer in the squeezing section leaves the extruder in the liquid phase and not as steam. In a less preferred embodiment, up to 20% by weight of the water removed in this section emerges as steam.
  • the squeezing section is provided with one or more drainage openings, which are generally under normal pressure. "Under normal pressure” means that the water exits the drainage opening under atmospheric pressure.
  • watering holes are preferably located on the top of the extruder, but side or downward arrangements are also possible. Furthermore, the drainage openings are preferably provided with a device which prevents the conveyed graft polymer A) from escaping. Especially before -
  • the drainage openings are designed in a manner known per se. Dewatering orifices are preferably used, the dimensions of which are selected such that the orifices cannot be blocked by the extruder contents. Cut-outs or bores in the extruder barrel (housing) are particularly preferably used as drainage openings.
  • no strainer housings or similar, quickly blocking components such as sieves are used as drainage openings.
  • strainer housings are susceptible to blockages.
  • the drainage opening associated with the damming elements is usually at a distance of at least one screw diameter Ds crin ec ke, preferably in a range from 1 to 4 Ds cnecke »and very particularly preferably 1 to 2 D ⁇ crm corner / in front of the damming element, or in the case of several stowage elements, before the first
  • the temperature of the exiting water is generally 45 20 to 95 ° C and preferably 25 to 70 ° C, measured at the outlet opening.
  • the first squeezing section depending on the elastomer component and the residual water content initially present, Usually 10 to 90, preferably 20 to 80% by weight of the residual water initially contained are removed.
  • the extruder is not heated in the metering sections and in the squeezing sections. In one embodiment, the extruder is cooled in these sections.
  • the partially 'dewatered graft polymer A) is about the congestion zones transported away and passes into the next extruder section.
  • the first squeeze section just described is followed by a second squeeze section, which in turn consists of a conveying section and a stowage zone which acts as an obstacle.
  • a second squeeze section which in turn consists of a conveying section and a stowage zone which acts as an obstacle.
  • the squeezed water usually leaves the extruder through all the drainage openings. Depending on the properties of the elastomer component and its residual water content, however, it is also possible that the squeezed water only exits from one or some of the available drainage openings, and the other drainage openings are "dry", that is to say that no or virtually no water is discharged. This has in no way proven to be disadvantageous.
  • squeezing The portion of the residual water that is not mechanically removed by squeezing (“squeezing") can be removed in the usual way via degassing devices of the extruder as steam.
  • At least 30% by weight of the residual water (which may, for example, adhere to the outside and / or be enclosed in the graft polymer A) is preferably pressed out as liquid water in the extruder.
  • 30 to 90% by weight of the residual water in liquid form is removed by squeezing and 10 to 70% by weight via degassing devices as steam.
  • the polymer B) and, if present, the polymers C), D) and / or E) are fed in in the form of a polymer melt.
  • the supply of the polymer melt can be done using an extruder or technically simpler conveying devices such as melt pumps or dosing screws.
  • the polymer melt from B) is fed to the extruder after the squeezing sections.
  • the mixture of squeezed-out, not yet melted graft polymer A) and polymer melt B) is melted and homogenized in subsequent sections which contain mixing, kneading and / or other plasticizing elements.
  • an extruder is used as a mixing device for components A) and B) and - if included - C), D), E) and F), as is generally known, the various zones of an extruder can be individually heated or cooled, to set an optimal temperature profile along the screw axis.
  • the person skilled in the art is also familiar with the fact that the individual sections of the extruder can usually be of different lengths.
  • the individual temperatures and lengths of the individual sections differ depending on the chemical and physical properties of components A) and B), and - if included - C), D), E) and F) and their proportions.
  • a rotational speed of the extruder screws in the range from 100 to 350 min " 1 may be mentioned only as an example.
  • the essentially molten polymer mixture produced in the mixing device from components A) and B) and - if present - C), D), E) and F) is subjected to rapid cooling according to the invention.
  • the rapid cooling usually takes place by contacting the essentially molten polymer mixture (hereinafter referred to briefly as "polymer melt”) with a cold medium or with a cold surface.
  • polymer melt essentially molten polymer mixture
  • Cold means a temperature which is so far below the temperature of the polymer melt that the polymer melt cools down rapidly when brought into contact. “Cold” therefore does not always mean chilled.
  • a 200 ° C hot polymer melt can be subjected to rapid cooling by water, which has previously been heated to, for example, 30 to 90 ° C. It is crucial that the difference between the polymer melt temperature temperature and the temperature of the cold medium or cold
  • “Fast” means that the polymer melt is converted from the molten state into the solid state and cooled in a period of 0 to 10 sec, preferably 0 to 5 sec and particularly preferably 0 to 3 sec.
  • the polymer melt is preferably rapidly cooled using a cold medium.
  • a cold medium can be gases or liquids.
  • the cooling gas is usually blown onto the polymer melt emerging from the mixing device.
  • Organic and inorganic cooling liquids can be used as liquid cold media (hereinafter referred to as "cooling liquid”).
  • Suitable organic cooling liquids are, for example, oils and other high-boiling organic liquid substances that do not have any chemical or physical interactions with the polymer melt to be cooled (e.g. swelling, dissolving, etc.), i.e. are chemically and physically inert to the polymer melt.
  • Inorganic cooling liquids are preferably used, in particular aqueous solutions and water.
  • Water which can be used in a cooled state (freezing point to room temperature), uncooled or at a temperature (room temperature to boiling point) is particularly preferred.
  • the coolant is usually sprayed onto the emerging polymer melt; or the polymer melt emerges from the mixing device directly into a bath from the cooling liquid.
  • the cooling liquid can also be applied to the emerging polymer melt as a broad jet of liquid (gush).
  • Spraying the polymer melt with cooling liquid is particularly advantageous when using mixing devices which produce foils (for example roller mills, mixing roll mills and calenders).
  • the polymer melt emerging as a film solidifies by spraying with cooling liquid to form a film.
  • the polymer melt particularly preferably emerges from the mixing device directly into a bath of the cooling liquid, very particularly preferably into a bath of water.
  • the polymer melt emerging from the mixing device is first brought into contact with a cooling glass, e.g. Inflation of tempered air or a protective gas such as nitrogen gas, cooling only slightly.
  • a cooling glass e.g. Inflation of tempered air or a protective gas such as nitrogen gas
  • the actual rapid cooling then takes place by bringing the melt previously solidified on the surface into contact with a cooling liquid, e.g. Water, whereby the interior of the melt also hardens.
  • the strands of the polymer melt emerging from the die head of the extruder can first be solidified on the surface by blowing air and the strands can then be transferred to a water bath, where the actual, rapid cooling takes place.
  • the polymer melt solidified by the rapid cooling can be processed further in a manner known to the person skilled in the art.
  • the solidified polymer is comminuted by grinding, cutting, granulating or other processes.
  • the rapid cooling and comminution is carried out using the underwater pelletizing method.
  • the polymer melt emerges from the mixing device through a nozzle plate, the bores (nozzles) of which are preferably round and which are preferably arranged in a circle.
  • the nozzle plate is under water (or another coolant) or the nozzle plate is sprayed with water (or another coolant), which can be done under protective gas.
  • nozzle plate Immediately behind the nozzle plate on the outside there are cutting devices, preferably rotating knives, which separate the emerging polymer.
  • the polymer is accordingly separated from rotating knives and quickly cooled in water (or another cooling liquid), where it solidifies to more or less round, pear-shaped grains.
  • a so-called underwater strand pelletizer is used.
  • the melt emerges as a strand from a nozzle plate and is immediately wetted by a surge of water or coolant and thereby cooled rapidly, after which the strands are introduced into a water bath or coolant bath over an inclined plane and granulated after cooling.
  • an extruder is used as a mixing device for components A) and B) and - if included - C), D), E) and F), with the underwater pelletizer just described.
  • the discharge opening of the extruder is consequently a submerged (or sprayed with water) nozzle plate with cutting devices, in particular rotating knives.
  • thermoplastic molding compositions comprising the components A) and B) described above, and — if present — C), D), E) and F) and butadiene as conjugated diene all) obtainable from
  • thermoplastic molding compositions according to the invention can be processed by the known methods of thermoplastic processing, e.g. by extrusion, injection molding, calendering, blow molding, pressing or sintering.
  • the molding compositions according to the invention have good mechanical properties, in particular good toughness, also good cold toughness, and a balanced ratio of toughness and rigidity. They show an improved tough-brittle transition.
  • the molding compounds have a low intrinsic color (yellowness index YI £ 25) as well as a low tendency to yellowing and yellowing only after a long period of heat storage or due to processing in the heat.
  • the molding compounds are further characterized by a high depth of color during the coloring (low light scatter with scatter values ⁇ 4.9).
  • Variant 0 The initial charge contained 1% by weight of TDM, the total amount of styrene or n-butyl acrylate (if these comonomers were used) and so much butadiene that the initial charge accounted for 16.6% by weight of the total amount of monomer . 1 hour after the start of polymerization, the remaining butadiene was metered in over 5 hours. The TDM was dosed in one portion at the start of the polymerization.
  • Variant 1 The total amount of styrene and 20% by weight of butadiene and 20% by weight of TDM were presented. The remaining 80% by weight of the butadiene was metered in over the course of 5 hours, with 20% by weight of the remaining TDM being added per hour.
  • Variant 2 Like variant 0, with the TDM being dosed in 3 equal portions at the beginning, in the middle and at the end of the residual butadiene inflow phase.
  • Variant 3 Like variant 0, but with 1.2 wt.% TDM.
  • Variant 4 Like variant 0, with an additional 0.5% by weight of TDM being metered in 10 minutes after the start of the residual butadiene feed.
  • Variant 5 As variant 4, but the initial charge contained only enough butadiene to make up 12.5% by weight of the total amount of monomer.
  • Variant 6 Like variant 3, but the template contained only enough butadiene that the template made up 12.5% by weight of the total amount of monomer.
  • Variant 7 As variant 3, the template additionally containing 0.2% by weight of butanediol diacrylate.
  • Variant 8 A seed latex containing polystyrene particles of a dso particle size of 29 nm, water, buffer salts and potassium persulfate (solids content 33%) was presented in such an amount that a
  • Butadiene contained 16.6% by weight of the total amount of monomers. The remaining butadiene was then metered in over the course of 6.5 hours, 0.33% by weight of TDM being added after 2.5 hours and after 6.5 hours.
  • Graft variant 1 8970 g of the graft monomer mixture given in Table 2 was added at 75 ° C. in the course of 4 hours with stirring.
  • Graft variant 2 The total amount of the graft monomer mixture given in Table 2 was 8970 g. So much styrene was first added at 75 ° C. while stirring that the amount of styrene made up 30% by weight of the total amount of the graft monomers. After a waiting time of 30 minutes, a monomer mixture of the remaining amount of styrene and the total amount of acrylonitrile or methyl methacrylate was added within 2 hours.
  • Graft variant 3 Like graft variant 1, with 0.5% by weight of TDM being added to the monomer mixture.
  • Particle size distribution had an average particle size dso of 150 to 350 nm and a dgrj value of 400 to 600 nm.
  • a first maximum of the particle size distribution was in the range 50 to less than 150 nm, a second maximum in the range 200 to 600 nm.
  • the density of the smaller graft polymer particles was 0.90 to 0. 93 g / cm 3 , the density of the large particles (second maximum 200 to 600 nm) at 0.96 to 0.98 g / cm 3 .
  • the dispersion obtained was mixed with an aqueous dispersion of an antioxidant and then coagulated by adding a magnesium sulfate solution.
  • the coagulated rubber was centrifuged off from the dispersion water and washed with water.
  • a rubber with about 30% by weight of adhering or enclosed residual water was obtained.
  • Table 2 Grafting pads and finished graft polymer A)
  • thermoplastic polymers B) to E) were produced by the process of continuous solution polymerization, as described in the plastics manual, ed. R. Vieweg and G. Daumiller, volume V "Polystyrene", Carl Hanser Verlag, Kunststoff 1969, p. 122 - 124, is described. Table 3 summarizes the compositions and properties.
  • Component El is a copolymer of 63% by weight of styrene, 13% by weight of acrylonitrile and 25% by weight of N-phenylmaleimide with a Vicat B heat resistance of 144 ° C.
  • Component E2 is a copolymer of 59% by weight of styrene and 41% by weight of N-phenylmaleimide.
  • the graft rubber A) containing residual water was dried with warm air in a vacuum and with the other components B) to F) in an extruder, type ZSK 30, from Werner and Pfleiderer, at 250 ° C. and 250 min -1 with a throughput of 10 kg / h, the molding compound was extruded and the molten polymer mixture was subjected to rapid subjected to cooling by introducing it into a water bath at 30 ° C.
  • the solidified molding compound was granulated.
  • the graft rubber A) containing residual water was metered into an extruder type ZSK from Werner and Pfleiderer, the two screw conveyors in the front part of which were provided with pressure-building dam elements. A considerable part of the residual water was mechanically pressed out in this way and left the extruder in liquid form through drainage openings.
  • the further components B) to F) were fed to the extruder in the form of their melts downstream behind the accumulation zones and mixed intimately with the dewatered component A). The remaining water was removed as steam via vent openings in the rear part of the extruder.
  • the extruder was operated at a speed of 250 min "1 and a throughput of 80 kg / h or 250 kg / h, the diameter of the extruder used - screw was chosen accordingly.
  • the molding compound was extruded and the molten polymer mixture was subjected to rapid cooling.
  • the rapid cooling was carried out in Examples 7 to 28 by underwater granulation with an underwater granulator from GALA: the die plate of the extruder was under water at a water temperature of 60 ° C.
  • the polymer emerging in the water bath as melt strands was separated from rotating knives which were located directly on the outside of the nozzle plate. Pearl-shaped polymer grains were obtained.
  • Swelling index of the graft base a film was produced from the aqueous dispersion of the graft base by evaporating the water. 0.2 g of this film was mixed with 50 g of toluene. After 24 hours the toluene was aspirated from the swollen sample and the sample weighed out. After drying the sample in vacuo at 110 ° C. for 16 hours, it was weighed out again. The following were calculated:
  • the average particle size d is the weight average of the particle size, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z. Polymers 250 (1972) pages 782 to 796.
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
  • the dirj value indicates the particle diameter at which 10% by weight of all particles have a smaller and 90% by weight a larger diameter. Conversely, for the dgo value it applies that 90% by weight of all particles have a smaller and 10% by weight larger diameter than the diameter which corresponds to the dgo value.
  • T time the T2 time was measured by measuring the NMR relaxation of a dewatered and film-coated sample. For this purpose, the sample was dried in vacuo for 3 hours at 60 ° C. and flashed off with a minispec device from Fa. Measure the brucker at 80 ° C. 5
  • Yellowness index YI the yellowness index YI was determined by determining the color coordinates X, Y, Z according to DIN 5033 under standard light D 65 and 10 ° normal observer using the following definition equation: 10
  • Viscosity number VZ it was determined according to DIN 53726 on a 0.5% by weight solution of the polymer in dimethylformamide. 15
  • Melt index MVR it was determined according to DIN 53735/30 at 220 ° C melting temperature and 10 kg or 21.6 kg load.
  • test specimens were produced from the granulate by injection molding, namely standard small bars (see DIN 53453), shoulder bars, round disks with a diameter of 60 mm and 2 mm thickness, or rectangular disks with a thickness of 2 mm.
  • the melt temperature was 250 ° C. in each case and the mold temperature in each case 60 ° C., unless stated otherwise.
  • Gloss it was determined according to ISO 2813 on rectangular panes 40 x 60 mm at 45 ° angle of incidence using the micro-gloss measuring device from Byk.
  • the Charpy impact strength a was determined on standard small bars by impact bending tests according to ISO 179-2 / leA (S) at 23 ° C, 10 ° C and -30 ° C.
  • Vicat The heat resistance according to Vicat was determined on press platelets according to ISO 306 / B with a load of 50 N and a heating rate of 50 K / h.
  • step granules were produced from the granules by injection molding at 240 ° C. melt temperature and 80 ° C. mold temperature, the thinner step being 1 mm and the thicker step being 2 mm thick.
  • the step plates were measured with a VIS spectrophotometer (Ultrascan from Hunter) to determine the scatter and absorption both over white and black background. The specific absorption and scatter at the wavelengths in the range from 400 to 700 nm were calculated from these measurements using the BCS color measurement system.
  • Tables 4 to 7 The measurement results are summarized in Tables 4 to 7.
  • Tables 4 and 6 contain mixtures of different components A and different components B.
  • Table 5 contains mixtures of component A8 with different components B.
  • Table 7 contains a mixture according to the invention and, for comparison, a molding composition not according to the invention with the same rubber content.
  • the tables show that the molding compositions according to the invention have a low intrinsic color (small yellowness index below 25 and absorption below 0.1%) and are easy to color (light scattering below 4.9). At the same time, the molding compositions according to the invention are impact-resistant, even in the cold (high values for a n , a K and a D ), and their flowability can be adjusted within a wide range (MVR values).
  • Table 7 gives a direct comparison of two molding compositions with an identical rubber content of 30 + 0.1% by weight.
  • the molding composition of Example 34 according to the invention contains the SAN polymer B1 as a matrix polymer with a low acrylonitrile content of 25% by weight according to the invention.
  • the molding composition of Example 35V not according to the invention contains the acrylonitrile-rich polymer Dl with 33% by weight of acrylonitrile instead of the low-acrylonitrile polymer B1.
  • Example 34 has a significantly lower yellowness index (18.1 instead of 38.4) and at the same time has a significantly better impact strength (a ⁇ 21/19/8 kJ / m 2 instead of 17/12/6 kJ / m 2 23/10 / -30 ° C, a D 31 instead of 25 N / m at 23 ° C).
  • the impact strength of the molding compositions according to the invention is therefore not only comparable, but significantly better.
  • the reduction in intrinsic color achieved does not go hand in hand with a deterioration in the mechanical properties, but on the contrary, with their improvement.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une matière moulable contenant les composants A) à F) suivants: A) 5 à 80 % en poids d'un polymère greffé A) ayant une répartition granulométrique bimodale, B) 20 à 95 % en poids d'un polymère thermoplastique B) ayant un indice de viscosité compris entre 50 et 120 ml/g et éventuellement d'autres polymères thermoplastiques C), D) et/ou E) à base au moins d'un monomère vinylaromatique, et éventuellement d'adjuvants F). Ces derniers peuvent être obtenus par 1) production d'un polymère greffé A) selon le procédé de polymérisation en émulsion, 2) mélange du polymère greffé A) avec le polymère B) et les éventuels autres composants C), D), E) et/ou F), dans le mélangeur, ce qui permet d'obtenir un mélange polymérique sensiblement en fusion, 3) rapide refroidissement du mélange polymérique sensiblement en fusion.
PCT/EP1998/003836 1997-07-04 1998-06-23 Matiere moulable thermoplastique ayant une faible couleur propre WO1999001489A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP98938632A EP0993476B1 (fr) 1997-07-04 1998-06-23 Matiere moulable thermoplastique ayant une faible couleur propre
DE59803025T DE59803025D1 (de) 1997-07-04 1998-06-23 Thermoplastische formmassen mit geringer eigenfarbe
AU87285/98A AU8728598A (en) 1997-07-04 1998-06-23 Low individual color thermoplastic molding material
US09/446,982 US6323279B1 (en) 1997-07-04 1998-06-23 Low individual color thermoplastic molding material
BR9810666-0A BR9810666A (pt) 1997-07-04 1998-06-23 Composição termoplástica de moldagem, processo e uso para preparação da mesma, e, moldado
CA002294918A CA2294918A1 (fr) 1997-07-04 1998-06-23 Matiere moulable thermoplastique ayant une faible couleur propre
KR1020007000027A KR100361001B1 (ko) 1997-07-04 1998-06-23 고유 색이 거의 없는 열가소성 성형 재료
JP50626499A JP2002510349A (ja) 1997-07-04 1998-06-23 固有色をほとんど有さない熱可塑性成形材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19728629A DE19728629A1 (de) 1997-07-04 1997-07-04 Thermoplastische Formmassen mit geringer Eigenfarbe
DE19728629.1 1997-07-04

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WO1999001489A1 true WO1999001489A1 (fr) 1999-01-14

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EP (1) EP0993476B1 (fr)
JP (1) JP2002510349A (fr)
KR (1) KR100361001B1 (fr)
CN (1) CN1140551C (fr)
AR (1) AR012259A1 (fr)
AU (1) AU8728598A (fr)
BR (1) BR9810666A (fr)
CA (1) CA2294918A1 (fr)
DE (2) DE19728629A1 (fr)
ES (1) ES2172908T3 (fr)
TW (1) TW470755B (fr)
WO (1) WO1999001489A1 (fr)
ZA (1) ZA985868B (fr)

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EP1108732A1 (fr) * 1999-12-16 2001-06-20 Basf Aktiengesellschaft Procédé pour la production de matériaux thermoplastiques à moulage
WO2001083574A1 (fr) * 2000-05-03 2001-11-08 Basf Aktiengesellschaft Matieres moulables thermoplastiques presentant une resistance aux chocs amelioree
WO2002046304A2 (fr) * 2000-12-05 2002-06-13 Bayer Aktiengesellschaft Matieres a mouler thermoplastiques
EP1764392A1 (fr) * 2005-09-14 2007-03-21 Basf Aktiengesellschaft Composition thermoplastique pour objets moulés ayant une adhésion améliorée d'une couche métallique électrodéposée
DE102008015124A1 (de) 2007-05-16 2008-11-20 Bayer Materialscience Ag Schlagzähmodifizierte Polycarbonat-Zusammensetzungen
WO2008020012A3 (fr) * 2006-08-18 2011-05-05 Basf Se Matières à mouler thermoplastiques à base d'acrylnitrile, de styrol et de butadiène
US8400621B2 (en) 2005-12-21 2013-03-19 Ceva Sante Animale Egg examining device
US9617417B2 (en) 2008-03-22 2017-04-11 Covestro Deutschland Ag Impact-modified polycarbonate compositions having a good combination of natural color, hydrolytic stability and melt stability

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EP1108732A1 (fr) * 1999-12-16 2001-06-20 Basf Aktiengesellschaft Procédé pour la production de matériaux thermoplastiques à moulage
US6515079B2 (en) 1999-12-16 2003-02-04 Basf Aktiengesellschaft Preparation of thermoplastic molding compositions
WO2001083574A1 (fr) * 2000-05-03 2001-11-08 Basf Aktiengesellschaft Matieres moulables thermoplastiques presentant une resistance aux chocs amelioree
US6835775B2 (en) 2000-05-03 2004-12-28 Basf Aktiengesellschaft Thermoplastic molding compounds with improved impact resistance
WO2002046304A2 (fr) * 2000-12-05 2002-06-13 Bayer Aktiengesellschaft Matieres a mouler thermoplastiques
WO2002046304A3 (fr) * 2000-12-05 2002-08-15 Bayer Ag Matieres a mouler thermoplastiques
EP1764392A1 (fr) * 2005-09-14 2007-03-21 Basf Aktiengesellschaft Composition thermoplastique pour objets moulés ayant une adhésion améliorée d'une couche métallique électrodéposée
WO2007031543A1 (fr) * 2005-09-14 2007-03-22 Basf Se Compositions de moulage thermoplastique ayant une meilleure adhérence d'un dépôt électrolytique de métal
US8400621B2 (en) 2005-12-21 2013-03-19 Ceva Sante Animale Egg examining device
WO2008020012A3 (fr) * 2006-08-18 2011-05-05 Basf Se Matières à mouler thermoplastiques à base d'acrylnitrile, de styrol et de butadiène
EP2949699A1 (fr) * 2006-08-18 2015-12-02 Styrolution Europe GmbH Procédé de préparation de masses de moulage thermoplastiques à base d'acrylonitrile, styrène et butadiène comprenant un copolymère thermoplastique et un copolymère greffé
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US9617417B2 (en) 2008-03-22 2017-04-11 Covestro Deutschland Ag Impact-modified polycarbonate compositions having a good combination of natural color, hydrolytic stability and melt stability

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CA2294918A1 (fr) 1999-01-14
US6323279B1 (en) 2001-11-27
JP2002510349A (ja) 2002-04-02
BR9810666A (pt) 2000-09-26
EP0993476A1 (fr) 2000-04-19
EP0993476B1 (fr) 2002-02-06
ES2172908T3 (es) 2002-10-01
CN1140551C (zh) 2004-03-03
ZA985868B (en) 2000-01-10
DE59803025D1 (de) 2002-03-21
KR20010021502A (ko) 2001-03-15
DE19728629A1 (de) 1999-01-07
CN1269808A (zh) 2000-10-11
AU8728598A (en) 1999-01-25
AR012259A1 (es) 2000-09-27
KR100361001B1 (ko) 2002-11-22
TW470755B (en) 2002-01-01

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